CAJ | 학술논문

采用密度泛函理论(DFT),选取DMol3程序模块,对噻吩在M(111)(M=Pd, Pt, Au)表面上的吸附行为进行了探讨。通过对噻吩在不同底物金属上的吸附能、吸附构型、Mul iken电荷布居、差分电荷密度以及态密度的分析发现,噻吩在Pd(111)面上的吸附能最大, Pt(111)面次之, Au(111)面最小。吸附后,噻吩在Au(111)面上的构型几乎保持不变,最终通过S端倾斜吸附于top位；噻吩在Pd(111)及Pt(111)面上发生了折叠与变形,环中氢原子向上翘起,最终通过环平面平行吸附于hol ow位。此外,噻吩环吸附后芳香性遭到了破坏,环中碳原子发生sp3杂化,同时电子逐渐由噻吩向M(111)面发生转移, M(111)面上的部分电子也反馈给了噻吩环中的空轨道,这种协同作用最终导致了噻吩分子稳定吸附于M(111)面。
채용밀도범함이론(DFT),선취DMol3정서모괴,대새분재M(111)(M=Pd, Pt, Au)표면상적흡부행위진행료탐토。통과대새분재불동저물금속상적흡부능、흡부구형、Mul iken전하포거、차분전하밀도이급태밀도적분석발현,새분재Pd(111)면상적흡부능최대, Pt(111)면차지, Au(111)면최소。흡부후,새분재Au(111)면상적구형궤호보지불변,최종통과S단경사흡부우top위；새분재Pd(111)급Pt(111)면상발생료절첩여변형,배중경원자향상교기,최종통과배평면평행흡부우hol ow위。차외,새분배흡부후방향성조도료파배,배중탄원자발생sp3잡화,동시전자축점유새분향M(111)면발생전이, M(111)면상적부분전자야반궤급료새분배중적공궤도,저충협동작용최종도치료새분분자은정흡부우M(111)면。
The adsorption of thiophene on Pd(111), Pt(111), and Au(111) surfaces was investigated by periodic density functional theory (DFT) calculations at the GGA/PW91 level. The results showed that the adsorption energies of thiophene on the different surfaces fol owing the order Pd(111)>Pt(111)>Au(111). The adsorption structure on the Au(111) surface showed almost no change, and the most stable adsorption structure was tilted adsorption on the top site through the S atom of thiophene. For the Pd(111) and Pt(111) surfaces, the most stable adsorption structure was paral el adsorption to the hol ow site through the ring plane of thiophene. After adsorption, the H atom of thiophene moved upward and the structure of thiophene was distorted and folded. The aromaticity of thiophene was disrupted and the C atoms were characteristic of sp3 hybridization. Furthermore, the electrons of the M(111) surfaces and thiophene were redistributed after adsorption. The electron transfer from thiophene to the M(111) surfaces was in the order Pd(111)>Pt(111)>Au(111). The electrons of the M(111) surfaces were also back-denoted to the empty orbitals of the thiophene molecule. These processes eventual y lead to the adsorption of thiophene on the M(111) surfaces.